Method of synthesizing covalently bonded lattices

Abstract

A method for the synthesis of multilayer γ-graphyne, an intrinsically semi-conducting sp 2 /sp 1 allotrope of carbon, through crystallization-assisted irreversible cross-coupling polymerization.

1 : A method comprising:
 synthesizing covalently bonded lattices based on irreversible bond-making reactions which favor exhaustive substitution on multi-functional substrates.   
     
     
         2 : The method of  claim 1 , wherein the bond-making reaction is a Sonogashira cross-coupling reaction between a terminal alkyne and an aryl halide. 
     
     
         3 : The method of  claim 2 , wherein a reactant of the Sonogashira cross-coupling reaction is a 1,3,5-trihalo-2,4,6-triethynylbenzene monomer, either symmetric or unsymmetric, where the halogen is any of Cl, Br, or I or a ((2,4,6-trihalobenzene-1,3,5-triyl)tris(ethyne-2,1-diyl))tris(trimethylsilane) monomer, either symmetric or unsymmetric, where the halogen is any of Cl, Br, or I. 
     
     
         4 . (canceled) 
     
     
         5 : The method of  claim 3 , wherein the Sonogashira cross-coupling reaction is performed using a palladium catalyst, and wherein a type of palladium source of the catalyst is selected from palladium black, palladium on carbon, palladium(π-cinnamyl) chloride dimer, bis(triphenylphosphine)palladium(II) dichloride, bis(benzonitrile)palladium(II) chloride, bis(triphenylphosphine)palladium(II) diacetate, tetrakis(triphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), dichlorobis(tricyclohexylphosphine)palladium(II), dichlorobis(tri-o-tolylphosphine)palladium(II), allylpalladium(II) chloride dimer, (2-methylallyl)palladium(II) chloride dimer, (1,3-bis(2,6-diisopropylphenyl)imidazolidene) (3-chloropyridyl) palladium(II) dichloride, (1,3-bis(2,6-dimethylphenyl)imidazolidene) (3-chloropyridyl) palladium(II) dichloride, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride, palladium(II) 2,4-pentanedionate, or any of the possible alkali metal salts of tris(3,3′,3″-phosphinidynetris(benzenesulfonato)palladium(0). 
     
     
         6 : The method of  claim 5 , wherein the Sonogashira cross-coupling reaction is performed using a copper co-catalyst and wherein the copper co-catalyst is selected from copper(I) iodide, copper(I) chloride, copper(I) bromide, tetrakis(acetonitrile)copper(I) hexafluorophosphate, tetrakisacetonitrile copper(I) triflate, copper(0) foil or shavings combined with pyridine, copper(0) foil or shavings combined with any aliphatic tertiary amine, or copper(II) sulfate combined with sodium ascorbate. 
     
     
         7 : The method of  claim 6 , wherein the reactant, palladium catalyst and copper co-catalyst are provided in a solvent and wherein the solvent is selected from pyridine, tetrahydrofuran, mixture of tetrahydrofuran and N,N-diisopropylethylamine, toluene, benzene, water, or biphasic mixtures of water and an immiscible organic solvent. 
     
     
         8 : The method of  claim 7 , wherein loading of the Pd catalyst is between 0.5 mol % and 120 mol % relative to the 1,3,5-trihalo-2,4,6-triethynylbenzene monomer and/or loading of the Cu co-catalyst is between 0.1 mol % and 10 mol % relative to the 1,3,5-trihalo-2,4,6-triethynylbenzene monomer. 
     
     
         9 . (canceled) 
     
     
         10 : The method of  claim 3 , wherein the reaction temperature is between 60° C. and 130° C. 
     
     
         11 : The method of  claim 3 , wherein the reaction is performed in the presence of a soluble fluoride salt. 
     
     
         12 : The method of  claim 1 , wherein ordered two-dimensional polymerization occurs in the absence of a physical substrate or added template. 
     
     
         13 : The method of  claim 1 , wherein the covalently bonded lattices include sp 2 /sp 1  allotropes of carbon. 
     
     
         14 . (canceled) 
     
     
         15 : The method of  claim 1 , wherein the covalent bonded lattices include γ-graphyne. 
     
     
         16 : The method of  claim 1 , yielding multilayer γ-graphyne with linear size of crystalline domains in the range of 10 nanometers to 500 micrometers. 
     
     
         17 : The method of  claim 1 , yielding 1 to 25 layers of γ-graphyne with linear size of crystalline flakes in the range of 10 nanometers to 500 micrometers. 
     
     
         18 - 33 . (canceled) 
     
     
         34 : Graphyne prepared by the process of  claim 1 . 
     
     
         35 : The graphyne of  claim 34 , having a substantially perfect crystal uniformity and/or substantially perfect hexagonal crystal symmetry. 
     
     
         36 : The graphyne of  claim 35 , having minimal or no crystalline defects. 
     
     
         37 : The graphyne of  claim 35 , having a 1:1 ratio of sp 1  to sp 2  carbons in the crystalline material. 
     
     
         38 : γ-Graphyne with linear size of crystalline domains in the range of 10 nanometers to 500 micrometers. 
     
     
         39 : The γ-graphyne of  claim 38 , including multifunctional reactive groups on edges of the γ-graphyne. 
     
     
         40 : The γ-graphyne of  claim 38 , wherein the multifunctional reactive groups are selected from alkyne and halo groups.